Catalyst based on aluminum fluoride for the gaseous phase fluorination of hydrocarbons

ABSTRACT

A CATALYST IS DISCLOSED FOR THE PREPARATION OF FLUORINATED HYDROCARBONS VIA FLUORINATION OF CHLOROFLUORINATION REACTIONS IN GASEOUS PHASE, THE CATALYST CONSISTING ESSENTIALLY OF ALUMINUM FLUORIDE CONTAINING MINOR, QUANTITIES OF IRON, CHROMIUM, AND PREFERABLY ALSO NICKEL COMPOUNDS, PRESENT IN QUANTITIES CORRESPONDING TO THE FOLLOWING PRECENTAGES BY WEIGHT OF THE METAL (BASED ON THE TOTAL): FROM 0.1% TO 5% OF FE, FROM 0.05% TO 8.5% AT LEAST PARTIALLY, IN THE FORM OF HALIDES, AND IN PARTICULAR FLUORIDES, OR IN THE FORM OF OXIDES OR OXY-HALIDES. THE CATALYST IS PREPARED BY ADDING IRON OR CHROMIUM COMPOUNDS, AND PREFERABLY ALSO NICKEL COMPOUNDS, IN A SUBDIVIDED FORM, TO ALUMINUM FLUORIDE OR ALUMINA, AND THEN SUBJECTING THE COMPOSITION THUS OBTAINED TO AN ACTIVATION TREATMENT BY HEATING AT A TEMPERATURE BETWEEN 300*C. AND 550*C. FOR FROM 0.5-4 HOURS IN A CURRENT OF NITROGEN OR AIR, AND THEN SUBJECTING SAID COMPOSITION TO A FLUORINATION TREATMENT BY HEATING AT 200*-500*C. IN AN HF CURRENT, SIUTABLY DILUTED WITH INERT GASES FOR THE THERMAL CONTROL OF THE REACTION, IN ORDER TO CONVERT, AT LEAST PARTIALLY, THE ALUMINA AND POSSIBLY ALSO THE OTHER METAL COMPOUNDS INTO THEIR RESPECTIVE FLUORIDE. THE CATALYST THUS OBATAINED IS IMPLOYED FOR THE FLUORINATION IN GASEOUS PHASE AT ELEVATED TEMPERATURES OF HALOGENATED ETHANES CONTAINING AT LEAST ONE CHLORINE ATOM, IN ORDER TO OBTAIN HIGH YIELDS IN FUORINATED ETHANES HAVING A HIGH DEGREE OF SYMMETRY, BY MEANS OF HF, OR FOR THE CHLOROFLUORINATION IN GASEOUS PHASE AT ELEVATED TEMPERATURES OF ETHYLENE OR PARTIALLY HALOGENATED ETHYLENES BY MEANS OF A MIXTURE OF HF+CL2, IN ORDER TO OBTAIN FLUORINATED OR CHLOROFLUORINATED ETHANES WITH A HIGH DEGREE OF SYMMETRY.

United States Patent 3,650,987 CATALYST BASED ON ALUMINUM FLUORIDE FOR THE GASEOUS PHASE FLUORINATION 0F HYDROCARBONS Martino Vecchio, Giovanni Groppelli, and Vittorio Fattore, Milan, Italy, assignors to Montecatini Edison S.p.A., Milan, Italy No Drawing. Filed July 18, 1969, Ser. No. 843,232 Claims priority, application Italy, July 25, 1968, 19,448/68 Int. Cl. B01j 11/78 US. Cl. 252-442 2 Claims ABSTRACT OF THE DISCLOSURE A catalyst is disclosed for the preparation of fluorinated hydrocarbons via fluorination of chlorofluorination reactions in gaseous phase, the catalyst consisting essentially of aluminum fluoride containing minor quantities of iron, chromium, and preferably also nickel compounds, present in quantities corresponding to the following percentages by weight of the metal (based on the total): from 0.1% to of Fe, from 0.05% to 8.5% of Cr, and up to 5% of nickel. These metals are present, at least partially, in the form of halides, and in particular fluorides, or in the form of oxides or oxy-halides. The catalyst is prepared by adding iron or chromium compounds, and preferably also nickel compounds, in a subdivided form, to aluminum fluoride or alumina, and then subjecting the composition thus obtained to an activation treatment by heating at a temperature between 300 C. and 550 C. for from 0.5-4 hours in a current of nitrogen or air, and then subjecting said composition to a fluorination treatment by heating at 200-500 C. in an HF current, suitably diluted with inert gases for the thermal control of the reaction, in order to convert, at least partially, the alumina and possibly also the other metal compounds into their respective fluorides. The catalyst thus obtained is employed for the fluorination in gaseous phase at elevated temperatures of halogenated ethanes containing at least one chlorine atom, in order to obtain high yields in fluorinated ethanes having a high degree of symmetry, by means of HP, or for the chlorofluorination in gaseous phase at elevated temperatures of ethylene or partially halogenated ethylenes by means of a mixture of HF+Cl in order to obtain fluorinated or chlorofluorinated ethanes with a high degree of symmetry.

The present invention relates to new catalysts for the fluorination in gaseous phase of halogenated hydrocarbons and for the chlorofluorination of ethylene.

These new catalysts are characterized by the fact that they facilitate the formation of greater quantities of symmetrical compounds or of compounds with a relatively higher degree of symmetry than those which are ob tained by means of known catalysts. The degree of symmetry in the present case refers to the distribution of the fluorine atoms and it is also understood that a not exactly symmetric compound, such as CF ClCFCl has a degree of symmetry greater than that of CF CCI Catalysts based on metal compounds for the gaseous phase fluorination of halogenated hydrocarbons are widely known. In particular, British Pat. No. 980,059 suggests a catalyst based on iron oxide and oxides of metals of the rare earths which is alleged to have the property of reducing the secondary disproportionation reactions which generally accompany the fluorination in gaseous phase. From Example 5 of that patent it appears that in the fluorination of 1,1,2 trifluoro-1,2,2 trichloroethane a mixture of isomers of C F4Cl is obtained which contains 73% of symmetrical CClF -CClF However, one notes ice a very low transformation yield with respect to the startlllg material.

The catalyst according to the present invention, in contrast to that of the above cited British patent, has the advantage of being prepared by starting from cheap compounds, and furthermore, in the fluorination of trifluorotrichloroethane it allows one to obtain symmetrical tetrafluorodichloroethane with a much higher yield with reference to the starting material.

The catalyst according to the present invention, in consists of aluminum fluoride containing minor quantities of iron and chromium compounds and preferably also of nickel, which compounds have been uniformly distributed on the aluminum fluoride granules, tfor instance, by treating the fluoride itself with solutions of salts of the above-mentioned metals.

The quantities of iron, chromium and nickel compounds introduced into the catalytic composition based on aluminum fluoride must be such as to fall within the following limits:

from 0.1% to 5% by weight, on the total, of iron (Fe) from 0.05% to 8.5% by weight, on the total, of chromium (Cr) up to 5% by weight, on the total, of nickel (Ni) Instead of aluminum fluoride for the preparation of the catalyst, one may use alumina which, during a subsequent fluorination treatment of the catalytic composition with gaseous HP, is substantially transformed into the fluoride. When using alumina for the preparation of the catalyst, it will be necessary to employ the iron compounds, the chromium compounds and the nickel compounds in greater proportions, that is, in proportions towards the higher percentages of the above-indicated ranges.

The iron, the chromium and the nickel are introduced into the catalytic composition-based on aluminum fluorideprefera'bly in the form of solutions of their salts, such as for instance the nitrates and the chlorides, which are absorbed by the aluminum fluoride or by the starting alumina. The composition thus obtained is dried in an oven at about C.

In the preparation of the catalyst one preferably uses iron, chromium and nickel compounds in the form of their halides or other compounds, in particular nitrates, which, after the activation treatments and the fluorination treatments of the catalytic composition, are then at least partially present in the form of the halides, in particular the fluorides, or oxides or oxy-halides.

The catalyst compositions based on aluminum fluoride or alumina, to which have been added the other metal compounds as aforesaid, are then subjected to an activation treatment and subsequently to a fluorination treatment. The activation treatment is carried out 'by heating up the product in an air or nitrogen current for a period of from 0.5 to 4 hours, and at a temperature between 300 and 550 C. When the catalyst is prepraed by starting from alumina, temperatures relatively greater than those in the case of aluminum fluoride are required.

The fluorination treatment is carried out by heating up the activated product in a current of gaseous HF conveniently diluted with air or nitrogen or other inert gas, and at a temperature between 200 and 500 C.

The catalyst thus obtained, in the form of fine granules, is particularly suited for use in fluid-bed reactors.

In the first example hereinafter the catalyst preparation is carried out starting from alumina, While in the second example it is carried out starting from aluminum fluoride.

It has been observed that the iron may be introduced into the catalytic composition during the fluorination reaction of the hydrocarbons; such a method of operating is illustrated in Examples 6, 7, 8 and 9 below. These working procedures are particularly convenient when one operates at high temperatures. In fact, in such a case the iron halides are rather volatile under the reaction conditions and the catalyst tends to become less selective if it is not supplied with further iron.

When carrying out the fiuorination reaction in a reactor made of an alloy containing Fe, Ni, Cr, for example Inconel, owing to the erosion of the alloy during the reaction a portion of the metals of the alloy goes over the aluminum fluoride (or fiuorinated alumina). This quantity of metals may already be suflicient for activating the catalytic composition.

The catalyst according to the present invention has proved particularly useful in the following reactions:

(a) Fluorination in gaseous phase with HF, of halogenated ethanes containing at least one chlorine atom, at a temperature between 360 and 500 C., for obtaining fiuorinated or chlorofluorinated ethanes with high yields of compounds having a high degree of symmetry with respect to the fluorine atoms. In particular, the fiuorination of CBCl-CFCI whereby high yields of the symmetrical CF ClCF Cl product and a reduced isomerization 'of the starting compound into CF CCl are obtained.

(b) Chlorofluorination of ethylene in a gaseous phase, with a Cl +HF mixture, in the presence of recycled halogenated hydrocarbons, at a temperature between 360 and 500 C., for obtaining predominately C F Cl and C F Cl with high percentages of isomers thereof having a high degree of symmetry, that is, CF ClCF Cl and (c) Disproportionation reaction of CF ClCFCl in gaseous phase, at a temperature between 360 and 500 C., with the formation of large quantities of the symmetrical CF Cl-CF Cl compound and very small quantities of the CF CCl isomer.

The use of the catalysts made according to the present invention, in the above-mentioned reactions, is illustrated below in Examples 3, 4, 5, 6, 7, 8 and 9 which are given for purely illustrative purposes.

EXAMPLE 1 Preparation of the catalyst starting from alumina 270 g. of Fe(NO -9H O and 65 g. of CrCl -6H O were dissolved in water at room temperature. This solution was then diluted up to a volume of 340 cc. which corresponds to the total volume of the pores of the alumina to be impregnated.

The solution was then slowly poured onto 1000 g. of grade A Ketjen alumina maintained under slow continuous stirring both during the impregnation as Well as for another two hours. Thereafter the solution and the alumina was left to rest for 4 hours and was then dried in an oven at 150 C. for 12 hours.

1 Chemical and physical characteristics of the alumina used Ketjen grade A alumina: of spheroidal shape Surface area280 mF/g. Volume of pores0.45 cc./

g. Apparent specific weight-029 g./cc.

Average composition: Percent A12 3 97.46 SiOs 1.80 NazO SO Fe 0.015

Loss at calcination at 450 C. for 4 hours 20%.

The granulometric distribution of the starting alumina, as determined by means of screens or sieves of the Tyler series, was the following The impregnated alumina was then poured into a reactor made of Inconel having a diameter of 11 cm. in

which, at a fiuidizing velocity of about 9 cm./sec., activation with air was carried out. Thereupon fiuorination with hydrofluoric acid was carried out according to the following procedure:

Activation: The treated alumina was heated in a stream of air, from 25 C. to 500 C. in 6 hours, then maintained at 500 C. for 30 minutes, and thereafter cooled from 500 to 300 C. in 1 hour, always under air flow.

Fluorination: Heating from 25 C. to 250 C. in 30 minutes under air flow, maintaining at 250 C. for 5 hours in a flow of air +1960 g. of HF, heating from 250 C. to 420 C. in 30 minutes under air flow, maintaining at 420 C. for 2 hr. 30 min. in a flow of air +1300 g. of HF, cooling from 420 C. to 250 in 30 minutes under air flow.

EXAMPLE 2 Preparation of the catalyst starting from AlF The catalyst was prepared by pouring the solution of active elements on aluminum fluoride which had the following chemical-physical characteristics:

content of fluorine: 64.2% and containing the following elements determined by means of an emission spectrograph:

By X-ray analysis the catalyst proved to consist of a-AIF with the presence of ,3-AlF It showed the following granulometric distribution, determined by means of a series of Tyler screens:

Mesh: Percent 325 12.8 Over 325 5.8

On 500 grams of this aluminum fluoride, under continuous slow stirring, was poured the solution of active elements; this latter was prepared by dissolving 41.2 g. of NiCl .6H O, 26.6 g. of CrCl .6H O and 37.7 g. of

in a minimum quantity of water heated up to 80 C., and by then diluting this solution up to a volume of 80 cc., which corresponds to the total volume of the pores of the aluminum fluoride to be impregnated. The mixture obtained was then left to rest for 4 hrs., after which it was dried at C. for 12 hours.

In an Inconel reactor of 4 cm. diameter was then carried out, at a fiuidizing velocity of about 9 cm./sec., the activation with air, and then the fiuorination with hydrofluoric acid according to the following procedures:

Activation: the treated aluminum fluoride was heated in a flow of nitrogen from 25 C. to 300 C. in 1 hour, then maintained at 300 C. for 1 hour, and thereafter cooled from 300 C. to 200 C. in 30 minutes, always under nitrogen flow.

Fluorination: maintaining at 200 C. for 1 hour in a flow of nitrogen+150 g. of HF, heating from 200 C.

to 420 C. in 30 minutes under nitrogen flow, maintaining at 420 C. for 30 minutes in a flow of nitrogen-H g. of HF, cooling from 420 C. to 250 C. in 30 minutes under nitrogen flow.

the disproportionation reaction of the CFzCl-CFClg with the formation of symmetrical products and for reducing the isomerization to CCl --CF Fluorination in gaseous phase of the CF Cl--CFCl 600 g. of A1 0 were first held in an oven at 120 C.

The fluorination reaction in this test was carried out in for 12 hours; h were then loaded mm an lncfml a nickel reactor containing a catalyst based on aluminum actor of i dlameter and were then heated up m alr fluoride, with a varying quantity of iron, chromium, flow.to 380 At thls temperatilre eqminolar mlxture nickel and vw-th an equimolar ratio of the HF and of air and anhydrous hydrofluoric acid was introduced for a period of 10 hours. Thereafter, the mixture was cooled 2 2 down in an air current and 720 g. of fluorinated alumina reactants. The reaction products were washed with water e F wlth thls flllOflnated alumina chloroand sodium hydroxide and were then condensed. The comfluermetlon tests on ethylene e then carried out by position of the mixture was determined by means of a eperatmg as m Example acme elements F P chromatograph and, as far as the isomers are concerned, on P catalyst the followmg W h r y by means of the LR absorption Spectra ducing the FeCl in the recycle which was in ected into the Table 1 records the results of the tests carried out both e and e C and N1, by placing AISI 316 bars inwith the catalyst according to the present invention as slde the reactor well as with other catalysts, in order to establish the char- Table 5 records the test commoner the composltlons of acteristic results achieved by the practice of this inventhe catalyst e the Produets obtamed- Table 6 records tion. the composition of the recycle.

EXAMPLE 4 EXAMPLES 8 AND 9 Chlorofluorination of ethylene 291 g. of CrC1 .6H O were dissolved in about 300 cc.

Tests of chlofofillol'lPatlon of ethylene 1T1 gaseous Phase of distilled water. 1500 g. of alumina were impregnated have been carried out in the presence of catalysts accordwith th l ti n thu obtained. Th product was then ing to this invention as well as in the presence of catalysts i d at 120 C, hil i i and was then l ft overdiiferent from these, in order to set up a comparison. The i ht i n e at 150 C. results of th s tests re c d below i Table 2- Fluorination of the catalyst: The thus-treated alumina For this purpose the tests were carried out in a nickel was then heated up to 250 C. in a reactor with a diamreactor containing catalyst based on aluminum fluoride eter of 1 0 cm. in a flow of air and, on reaching the abovewith varying quantities of iron, nickel, chromium, by inindicated temperature, there was then introduced a mixtroducing into the reactor the C H C1 and HF reactants ture of air and HF (30% of HF) for 7 hours. together with recycled products (chlorofluorinated hydro- The total quantity of HF amounted to 2540 g. Therecarbons) whose composition is reported in Table 3. The upon, the product was heated from 250 C. up to 420 C. reaction product was then subjected to distillation. The in a flow of air only. It was then further fluorinated at tail fraction was recycled into the reactor. The low boiling 420 C. with a mixture of air and HF (30% of HF) for fraction consisted of a mixture of C F Cl, C F Cl and 6 hours. The quantity of HF introduced into the reactor C F Cl The composition and the ratio between the variamounted to 1630 g. ous isomers are indicated in Table 2. Finally, the mass was cooled down from 420 C. to

200 C. in a current of air only. From the reactor were EXAMPLE 5 discharged 1470 g. of fluorinated alumina. Disproportionation and isoinerization of CFgCl-CFC12 Tests ffl of ethylene Were then carried out with this fluorinated alumina by following the Through a gl s e c eontalnlflg the Catalyst Was same operational procedures as described above in Exampassed CF Cl--CFCl in the gaseous state, at the operal 4, tional COIldltiOIlS indicated in Table 4. The reaction prod- The other two active elements were put on the catalyst ucts were then sent directly into a chromatograph in order b l i i th reactor ir n bar d b of A151 316, to determine the composition. and leaving them there during the tests.

From the r s rec in Table 1t f be Seen Table 7 records the test conditions, the catalyst comhow effective is the simultaneous presence of iron, chropositions and the products obtained; Table 8 records the mium and nickel in the aluminum fluoride for promoting compositions of the recycle.

TABLE 1 Test Number 1 2 3 4 5 6 7 8 9 10 11 12 13 Catalyst, percent:

Ni 0 2 o o 2 4 2 4 1 0.33 0 3 0.33 0020121210.38138.5 0 0 0 1 0 0 1 10-38041 1 10.5 Reaction temperature in C 4.00 400 400 400 400 400 420 430 400 400 400 400 400 Contact time in seconds 3 3 1. 5 3 3 3 3 3 3 3 3 2. 9 3 HF conversion, percent 83 86 82 35 79 46.9 56 55.9 64 31.6 33.2 CF Cl-OFCh conv., percent.-. 96 94 89 35 83 83 56 52 65 72 32.7 37.5 76.8 N ct yields in percent: 1

in 01 361 301-... 16 31 25 1.5 18 16 1 3.6 6.8 0 .3 .7 9 In oneron--- 2s 18 3 20 15 2 3.4 7.5 25.7 5.7 4.4 11.5 In CFzCl-CFz 16 37 64 46 as 86 76.2 52 s5 s4 67 InCF3CCl 23 16 9 0.1 7.7 a 0.1 0.1 2.1 4.9 0.2 1.6 4.3

1 The difierence to reach consists for the greatest part of C2F2Cl (mixture of isomers).

TABLE 2 Test Number 1 2 3 4 5 6 Catalyst, percent:

Ni 2 2 2 2 2 CL 0 0 1 1 1 1 Fe. 1 0 0 1 1 0. 33 1 Reaction temperature in C 400 400 400 420 400 380 Contact time in seconds. 1. 7 1. 1. 5 1. 5 1. 5 1. 5 Cl:/HF/C2I'I4 0.1/4.6/1 5/4.4/1 5. 3/4. 2/1 5. 3/4. 4/1 5/4. 1/1 4.3/4/1 C1lI4-recycle. 10 10/1 10/1 10/1 10/1 lO/l HF eonvcrsioi 8G. 3 88 74. 5 77 83 85 Net yields in percent:

In C2F5C 2. 4 1.8 Traces 1 Traces In C2F C] 80 74.1 0. 2 31. 6 01 37 In C2FaCl 10.4 23. 0 94 67 37 61 Selectivity in pe OF:ClCF2Cl/C2F4Cl2 11 24 65 54 52 61 CF2Cl-CFCl2/C:F3Cla. 56 45 08 93 85 J6 TABLE 3 Test Number 1 2 3 4 5 6 Composition of rccyclc in percent by weight:

0. 5 O. 5 Traces Traces 0. 3 Traces 11. 4 17 1. 2 2 5. 2 1 13. 4 14 45 20 27 22 0. 7 1. 4 1. 3 1. 1 Traces 2. 9 1. 5 0. 8 O. 6 Traces Traces 2. 7 22. 4 23. 6 22. 8 25. 9 36. 4 9. 1 43. 5 31. 2 25. 7 34. 8 20. 1 60. 5 5. 4 7. 5 3. 4 5. 7 8. 6 1 l. 6 3. 3 Traces 1. 4 2. 3 Traces TABLE 7 Example 8 9 TABLE 4 30 Catalyst composition in percent: 3 Test Number 1 2 3 4 5 N1 5 0. 84 0.15 Catalyst composition, percent. Reaction emperamre in o C 450 400 N1 4 2 Contact time in seconds 3 3 g; 2 cigar/(51%. Reaction iperaturc 111 400 400 400 gt flg ft g g Contact time in seconds. 3 3 3 3 30 Net yields in percent: Conversion in percent 99 97 99 22 52 C1 0' 1 0 1 Net yield in percent: 36 4 5 In CgF5Cl 4. 6 14. 8 12. 7 6. 4 3 63 2 85 1 1n C2F4C121 23. 7 13. 9 17 45 0. 3 In CF3-CG13 38. Q 27. 9 28 7. 3 0. 1 l t t In C2F2Cl4 32- 8 43- 9 3 50 0 CFZC1 CFZc1/C2F4C12 1 In Example 5, 70% of the 011M312 consists of CF2Cl-CFzCl. OM31 CF01 C1301 97 J TABLE 8 Example 8 9 45 Recycle corriilllosition M ,s in pcrcen y weig TABLL 5 C2 012 Traces Example 6 7 C F3 1:

Catalyst composition in percent: g g Ni 0.0 0.6 24 2 37 8 cac 1on enipera ure Contact time in seconds.. 3 3 Tmces 4 twee 435% 4.71

ecyc e z 4 HF conversion in percent 60 48 What 15 clalmed I Net m ld in p 3 1 1. A catalyst for the preparation of fiuorinated hydroipf ijj 95 3e 4 carbons by fluorination or chlorofiuorination reactions in g i g 3-? gaseous phase, consisting essentially of aluminum fluoride g i 'fl'fi f fi containing iron, chromium and preferably also nickel, es- CFzCl-OFzCl/CzF4Clz 67 77 CF2Cl-GFCl:/C2F Cl; 98.6 sefrlmally 1n the form of halides, Ox des or oxy halides,

w erein the quantltles of those metallic compounds correspond to the following percentages by weight of metal based on the total: from 0.1% to 5% of Fe, from 0.05% to 8.5% of Cr, and up to 5% of Ni.

2. A catalyst according to claim 1, wherein the halides TABLE 6 are the fluorides.

References Cited Example 6 7 UNITED STATES PATENTS Recycle composition in percent by 0 8 0 3 2,744,148 5/1956 Ruh et al. 252442 X P 3,294,852 12/1966 Vecchio et a1. 260653.7 68 3,342,881 9/1967 Sasakura et a]. 260653.7 Traces Traces Traces 0.

5.12 PATRICK P. GARVIN, Primary Examiner 0 0 1. 8 2. 0 Traces Traces US. Cl. X.R. 

